EP1337568B1 - Verfahren zur herstellung von wetterbeständigem thermoplastischen harz - Google Patents

Verfahren zur herstellung von wetterbeständigem thermoplastischen harz Download PDF

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Publication number
EP1337568B1
EP1337568B1 EP01274352A EP01274352A EP1337568B1 EP 1337568 B1 EP1337568 B1 EP 1337568B1 EP 01274352 A EP01274352 A EP 01274352A EP 01274352 A EP01274352 A EP 01274352A EP 1337568 B1 EP1337568 B1 EP 1337568B1
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Prior art keywords
weight parts
preparing
acrylate
thermoplastic resin
meth
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French (fr)
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EP1337568A1 (de
EP1337568A4 (de
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Yang-Hyun LG Chem Ltd. SHIN
Keun-Hoon Yoo
Tae-Bin Ahn
Chan-Hong Lee
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LG Chem Ltd
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers

Definitions

  • the present invention relates to a method for preparing thermoplastic resin having weatherability, and more particularly to a method for preparing thermoplastic acrylate-styrene-acrylonitrile (ASA) resin having excellent weatherability and color matching properties.
  • ASA thermoplastic acrylate-styrene-acrylonitrile
  • thermoplastic resin industry has advanced and the distinctiveness of goods model has gained popularity, research on giving high function of colorability etc, to materials used in the industry has progressed a great deal.
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin.
  • ABS resin has good qualities of impact resistance, processibility, and surface gloss, etc., it has a problem in that it is unsuitable for use outdoors due to bad weatherability and light resistance because of properties of the resin, and thermal stability is also bad, chemical resistance is weak, and its properties diminish over time.
  • ASA acrylate-styrene-acrylonitrile
  • Japanese Laid-Open Patent Publication No. Hei 5-202264 has suggested a method for improving properties by preparing ASA resin with a bimodal shape.
  • the method discloses that ASA resin with a small diameter of 50 ⁇ 200 nm, and ASA resin with a large diameter of 200 ⁇ 1000 nm each prepares, and then the two resins are latex blended together, and resultant blends with a separately prepared styrene-acrylonitrile (SAN) copolymer to produce ASA resin having superior weatherability.
  • SAN styrene-acrylonitrile
  • German Patent No. 1260135 has described the method in detail.
  • Japanese Laid-Open Patent Publication No. Hei 4-180949 discloses a method for preparing ASA resin by making multi-layer graft copolymer particles.
  • the method suggests a preparation of ASA resin for improving weatherabilty in which a hard core is first prepared by using a monomer having a high glass transition temperature, then a crosslinked acrylate rubber component is added, followed by a crosslinked shell of a styrene monomer, an acrylonitrile monomer having a high glass transition temperature, and a crosslinking agent, and finally by preparing a soft shell with an uncrosslinked styrene monomer and an acrylonitrile.
  • this method also does not mention a method capable of improving colorability and surface gloss of ASA resin.
  • ASA resin has weatherability, chemical resistance, and thermal stability, it has problems of a lowering colorabilty and surface gloss, wreak side impact strength, and its molding capacity is limited due to a low fluidity. Additionally, important technical difficulties to overcome in the preparation of ASA resin are known to be that colorability and surface gloss showing a pearl color etc. while color matching are reduced, and impact strength is low. Also, color dispersion falls due to properties of acrylate rubber.
  • the present invention is made in consideration of the problems of the prior art, and it is an object of the present invention to provide a method for preparing thermoplastic acrylate-styrene-acrylonitrile (ASA) resin having superior weatherability, as well as properties and colorability equal to ABS resin.
  • ASA thermoplastic acrylate-styrene-acrylonitrile
  • thermoplastic resin having superior impact resistance, chemical resistance, and surface gloss.
  • the present invention provides a method for preparing a weatherable thermoplastic resin as set forth in the appended claims.
  • the present invention also provides a weatherable thermoplastic resin prepared by the above method.
  • the present inventors continuously studied. As a result, the present invention was completed by introducing methylmethacrylate, by controlling contents of each component, by introducing a hard core during polyacrylate rubber polymerization, and by using a water-soluble initiator and an oil-soluble initiator differently in the polymerization steps to prepare ASA resin.
  • the resin of the present invention comprises an acrylonitrile giving superior chemical resistance, an acrylate-based rubber giving superior impact resistance, and a styrene giving superior processability, to prepare a thermoplastic resin having superior impact resistance, chemical resistance, processability, weatherability, colorability, and surface gloss.
  • thermoplastic resin having superior weatherability of the present invention comprises the steps of a) preparation of a seed, b) preparation of a crosslinked alkyl acrylate rubber polymer, and c) preparation of a graft copolymer, and each process is explained in more detail as follows.
  • the present invention prevents distortion of the rubber by hardening a rubber core through seed polymerization of 0.5 to 10 weight parts of an aromatic vinyl compound monomer or an alkyl(meth)acrylate monomer having a high glass transition temperature, based on 100 weight parts of the total monomers.
  • alkyl(meth)acrylate compounds examples include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, 2-ethyl hexyl(meth)acrylate, decyl(meth)acrylate and lauryl(meth)acrylate etc., and more preferable is methyl methacrylate.
  • the aromatic vinyl compound used is a styrene monomer derivative.
  • Preferable examples are selected from the group consisting of styrene, ⁇ -methyl styrene, and vinyl toluene, and particularly preferable is styrene.
  • a water-soluble initiator in the case of initial seed polymerization, a water-soluble initiator is used; and in the case of polymerization in second and third steps, an oil-soluble initiator is used, and thus colorability and surface gloss can be improved by increasing graft efficiency of the reactant.
  • the initiator used in the present invention is an inorganic or an organic peroxide.
  • the water-soluble initiator is used to improve colorability, and the oil-soluble initiator is used in the graft and rubber particle growth reaction.
  • the water-soluble initiator is preferably selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate, while the oil-soluble initiator is preferably cumene hydroperoxide, t-butyl hydroperoxide, or benzoyl peroxide.
  • the content of the water-soluble initiator is 0.05 to 0.2 weight parts based on 100 weight parts of total monomers.
  • the crosslinking agent used in the present invention is preferably selected from the group consisting of ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 1,3-buthanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, trimethylol propane trimethacrylate, and trimethylol methane triarylate.
  • the content is 0.05 to 0.3 weight parts based on 100 weight parts of total monomers.
  • An electrolyte used in the present invention is preferably selected from the group consisting of NaHCO 3 , Na 2 S 2 O 7 , K 2 CO 3 , and preferable is NaHCO 3 .
  • the content of electrolyte is 0.05 to 0.4 weight parts based on 100 weight parts of total monomers.
  • the present invention performs the step of preparing a crosslinked alkyl acrylate rubber polymer by adding an alkyl acrylate monomer; an aromatic vinyl compound, an alkyl(meth)acrylate, or a vinyl cyanide compound; a metal salt derivative of alkyl sulfosuccinate with C 12 ⁇ C 18 , or a metal salt derivative of alkyl sulfuric acid ester or metal salts of sulfonate with C 12 ⁇ C 20 , as an emulsifier; and the oil-soluble initiator, to the seed prepared in the a) step.
  • an alky acrylate monomer (preferably butyl acrylate) as a major monomer is used, and the content thereof is 5 to 45 weight parts based on 100 weight parts of total monomers.
  • the present invention preferably uses 1 to 5 weight parts of an optimized mixture ratio of methyl methacrylate, styrene, and acrylonitrile as a supplement to improve efficiency of the rubber particles and the pearl color, and it is also possible to copolymerize a functional monomer.
  • the functional monomer is selected from the group consisting of methacrylic acid, acrylic acid, maleic acid, itaconic acid, and fumalic acid.
  • An aqueous solution of the emulsifier preferably has pH of 3 ⁇ 9, and for example the emulsifier used is a metal salt derivative of alkyl sulfosuccinate with C 12 ⁇ C 18 , or a derivative of alkyl sulfuric acid ester or metal salts of sulfonate with C 12 ⁇ C 20 .
  • the metal salt derivative of alkyl sulfosuccinate with C 12 ⁇ C 18 is a sodium or potassium salt etc.
  • alkyl sulfate metal salts such as sodium lauric sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate, potassium octadecyl sulfate, etc.
  • sodium dioctyl sulfosuccinate or potassium dioctyl sulfosuccinate is preferable.
  • the content of emulsifier used is 0.2 to 1.0 weight parts based on 100 weight parts of total monomers.
  • a carboxylate metal salt derivative such as a metal salt of aliphatic acid or a metal salt of rosiniate etc. where an aqueous solution of the emulsifier has pH of about 9 ⁇ 13 is used, although drying can be enhanced, it is difficult to graft methacrylic acid methyl in the butyl acrylate rubber polymer into ASA resin due to a lower moisture content, and thus stripping occurs because of phase separation resulting in a substantial decrease in impact strength.
  • the oil-soluble initiator used in the present invention is preferably cumene hydroperoxide, t-butyl hydroperoxide, or benzoyl peroxide.
  • the content is 0,05 to 0.2 weight parts based on 100 weight parts of total monomers.
  • the b) step can further comprise a grafting agent selected from the group consisting of v) aryl methacrylate (AMA), triarylisocyanurate (TAlC), triarylamine (TAA), and diarylamine (DAA), wherein the content is 0.01 to 0.07 weight parts based on 100 weight parts of total monomers.
  • a grafting agent selected from the group consisting of v) aryl methacrylate (AMA), triarylisocyanurate (TAlC), triarylamine (TAA), and diarylamine (DAA), wherein the content is 0.01 to 0.07 weight parts based on 100 weight parts of total monomers.
  • the crosslinking agent used in the present invention is preferably selected from the group consisting of ethyleneglylcol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, 1,3-buthanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, trimethylol propane trimethacrylate, and trimethylol methane triarylate.
  • the content is 0.05 to 0.3 weight parts based on 100 weight parts of total monomers,
  • the electrolyte used in the present invention is preferably selected from the group consisting of NaHCO 3 , Na 2 S 2 O 7 , and K 2 CO 3 , and NaHCO 3 is preferable.
  • the content of electrolyte is 0.05 to 0.4 weight parts based on 100 weight parts of total monomers.
  • the reaction can be performed only through emulsion polymerization, or it can be preformed by suitably mixing emulsifier-free emulsion polymerization and emulsion polymerization to prepare acryl rubber polymer latex.
  • the monomers can be added continuously, or by adding continuously and in batches.
  • the aqueous solution of the crosslinked alkyl acrylate rubber polymer latex after polymerization of the present invention preferably has pH of 5 to 9, and more preferably 6 to 8.
  • the rubber polymer preferably has a diameter of 2500 ⁇ 5000 ⁇ , and more preferably 3000 ⁇ 4500 ⁇ .
  • the present invention can have improved impact strength and it can maintain colorability of ASA resin better when compared to the prior art through the graft reaction by adding an aromatic vinyl compound, a vinyl cyanide compound, metal salts of rosinate or metal salts of carboxylate with C 12 ⁇ C 20 as an emulsifier, and an oil-soluble initiator to the acrylate rubber polymer prepared in the b) step.
  • the monomer grafted in the crosslinked alkyl acrylate rubber polymer uses 10 to 40 weight parts of the aromatic vinyl compound and 1 to 20 weight parts of the vinyl cyanide compound, and a functional monomer is further used according to necessity.
  • the aromatic viny! compound used is a styrene monomer derivative. As an example, it is selected from the group consisting of styrene, ⁇ -methyl styrene, and p-methyl styrene, and preferable is styrene.
  • the vinyl cyanide used is acrylonitrile or methacrylonitrile, and preferable is acrylonitrile.
  • the functional monomer possibly used can be methacrylic acid, acrylic acid, maleic acid, itaconic acid, furmalic acid, etc.
  • the aqueous solution of the emulsifier preferably has pH of 9 ⁇ 13, and as an example the emulsifier is preferably a metal salt derivative of carboxylate such as a metal salt derivative of aliphatic acid with C 12 ⁇ C 20 , a metal salt of rosinate, etc.
  • the metal salt derivative of aliphatic acid is a sodium or potassium salt of a fatty acid, lauric acid, or oleic acid
  • the metal salt of rosinate is sodium rosinate or potassium rosinate.
  • a metal salt derivative of carboxylate such as a metal salt of aliphatic acid with C 12 ⁇ C 20 or a metal salt of rosinate etc. where the aqueous solution emulsifier has a pH of about 9 ⁇ 13 is used, as the pH of the total system rises little by little, a carboxyl group of butyl acrylate rubber polymer having a low glass transition temperature comes out of the particle.
  • a graft phase having a high glass transition temperature comes to the inner part of the butyl acrylate rubber polymer particle, and thus a surface glass transition temperature can be lowed and thereby it can be coagulated at normal pressure, and additionally, drying also becomes easier because the moisture content inside the ASA particle is remarkably decreased.
  • an oil-soluble initiator such as cumene hydroperoxide, t-butyl hydroperoxide, or benzoyl peroxide is used, and the content is preferably 0.05 to 0.2 weight parts based on 100 weight parts of total monomers.
  • the mixing monomer comprising an emulsifier is preferably continuously added.
  • the batch adding method since pH of the polymerization system rises at the same time, it is difficult to graft and the inner structure is not uniform due to inferior particle stability.
  • the final latex aqueous solution prepared by the method preferably has pH of 8 ⁇ 11, and more preferably 9 ⁇ 10.5. Additionally, a diameter of the rubber polymer latex is preferably 3000 ⁇ 6000 ⁇ , and more preferably 3500 ⁇ 4500 ⁇ .
  • a weatherable thermoplastic resin which has superior impact resistance, chemical resistance, processability etc., and improved colorability and surface gloss can be obtained by controlling an amounts of the monomer components such as an alkyl(meth)acrylate compound, an aromatic vinyl compound, a vinyl cyanide compound etc- added in a polyacrylate-based rubber latex, and particularly by graft polymerizing them together with a water-soluble initiator and an oil-soluble initiator.
  • the monomer components such as an alkyl(meth)acrylate compound, an aromatic vinyl compound, a vinyl cyanide compound etc- added in a polyacrylate-based rubber latex
  • ion exchange water 70 wt parts styrene (SM) 2 wt parts ethyleneglycol dimethacrylate (EDMA) 0.02 wt parts sodium bicarbonate 0.1 wt parts potassium persulfate (KPS) 0.01 wt parts
  • the components were introduced into a polymerization reactor under a nitrogen atmosphere, and the temperature was elevated to 70 °C and they were reacted for 1 hour.
  • the diameter of the obtained latex was 4000 ⁇ , the pH thereof was 8, and a polymerization conversion rate was 98%.
  • the diameter of the latex was measured by the dynamic laser-light scattering method using a Nicomp analyzer (Model: 370HPL).
  • the obtained latex was coagulated at 85 °C, normal pressure with a calcium chloride aqueous solution, then aged at 95 °C, then dehydrated and washed, and finally dried by hot blast at 90 °C for 30 min. to obtain ASA powder particles having weatherability.
  • ASA powder particles having weatherability obtained by the method a SAN (81 HF) copolymer resin (LG CHEM. Ltd. product), an antioxidant and a photostabilizer were introduced, and the whole was kneaded and extruded at 200 to 250 °C to prepare a pellet having a rubber content of 20 %.
  • the pellet was injection molded again and the properties were measured, and the results are shown in Table 1.
  • the properties were measured by the ASTM method, and measurement conditions of each property were as follows.
  • ASA resin was prepared by the same method as in Example 1, except that the amount of styrene used in the first polymerization step was increased to 5 wt parts, and the amount of styrene used in the third polymerization step was reduced to 35 wt parts.
  • the properties were measured by the same method as in Example 1, and the results are shown in Table 1.
  • ASA resin was prepared by the same method as in Example 1, except that TBHP (t-butyl hydroperoxide was used instead of cumene hydroperoxide as the initiator in the second polymerization step.
  • TBHP t-butyl hydroperoxide was used instead of cumene hydroperoxide as the initiator in the second polymerization step.
  • the properties were measured by the same method as in Example 1, and the results are shown in Table 1.
  • ASA resin was prepared by the same method as in Example 1, except that methylmethacrylate was used instead of the styrene monomer in the first polymerization step.
  • the properties were measured by the same method as in Example 1, and the results are shown in Table 1.
  • ASA resin was prepared by the same method as in Example 1, except that acrylonitrile was used instead of the styrene monomer in the second polymerization step.
  • the properties were measured by the same method as in Example 1, and the results are shown in Table 1.
  • ASA resin was prepared by the same method as in Example 1, except that methylmethacrylate and the styrene monomer were not added in the second polymerization step, and the amounts thereof were added in the third step polymerization.
  • the properties were measured by the same method as in Example 1, and the results are shown in Table 1.
  • ASA resin was prepared by the same method as in Example 1, except that potassium persulfate (KPS) as a water-soluble initiator was used instead of cumene hydroperoxide (CHP) in the second and third polymerization steps.
  • KPS potassium persulfate
  • CHP cumene hydroperoxide
  • Examples 1 to 5 using both a water-soluble initiator and an oil-soluble initiator of the present invention had excellent impact strength at 16 ⁇ 20 Kg cm/cm, and surface gloss and colorability were very excellent.
  • Comparative Example 2 used only a water-soiuble initiator, and the thus-produced ASA resin had a very low impact strength, and colorability was extremely bad.
  • thermoplastic resin of the present invention results in a resin with superior impact resistance, chemical resistance, and processability, etc., and particularly a thermoplastic resin with good weatherability and having improved colorability and surface gloss can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (12)

  1. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz, das folgende Schritte aufweist, nämlich
    a) Herstellen eines Keimes durch Hinzufügen von 0,05 bis 0,2 Gewichtsanteilen eines wasserlöslichen Starters, 0,05 bis 0,3 Gewichtsanteilen eines Vernetzers und 0,05 bis 0,4 Gewichtsanteilen eines Elektrolyten zu 0,5 bis 10 Gewichtsanteilen von entweder einer aromatischen Vinylverbindung oder eine Alkyl(methyl)acrylat, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    und Polymerisieren derselben;
    b) Herstellen eines Alkylacrylatkautschukpolymers durch Hinzufügen von
    i) 5 bis 45 Gewichtsanteilen eines Alkylacrylatmonomers, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    ii) 1 bis 5 Gewichtsanteilen einer aromatischen Vinylverbindung, eines Alkyl(methyl)acrylates oder einer Vinylcyanidverbindung, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    iii) 0,2 bis 1,0 Gewichtsanteilen eines Metallsalzderivates eines Alkylsulfosuccinates mit C12 bis C18 oder eines Metallsalzderivates eines Alkylschwefelsäureesters oder Metallsalzen von Sulfonaten mit C12 bis C20 als Emulgator, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    iv) 0,05 bis 0,2 Gewichtsanteilen eines öllöslichen Starters, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    v) 0,05 bis 0,3 Gewichtsanteilen eines Vernetzers, basierend auf 100 Gewichtsanteilen der Gesamtmonomere, und
    vi) 0,05 bis 0,4 Gewichtsanteilen eines Elektrolyten, basierend auf 100 Gewichtsanteilen der Gesamtmonomere
    zu dem Keim und Polymerisieren derselben; und
    c) Herstellen eines thermoplastischen Harzes durch Hinzufügen von
    i) 10 bis 40 Gewichtsanteilen einer aromatischen Vinylverbindung, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    ii) 1 bis 20 Gewichtsanteilen einer Vinylcyanidverbindung, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    iii) 0,5 bis 3,0 Gewichtsanteilen von Metallsalzen von Kolophoniumderivaten oder Metallsalzen von Carboxylaten mit C12 bis C20 als Emulgator, basierend auf 100 Gewichtsanteilen der Gesamtmonomere, und
    iv) 0,05 bis 0,2 Gewichtsanteilen eines öllöslichen Starters, basierend auf 100 Gewichtsanteilen der Gesamtmonomere,
    zu dem Alkylacrylatkautschukpolymer und Durchführen einer Pfropfcopolymerisation.
  2. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach Anspruch 1, bei dem das in Schritt b) erhältliche Alkylacrylatkautschukpolymer einen Durchmesser von 2500 bis 5000 Å aufweist und eine wässrige Lösung des Polymers einen pH von 5 ∼ 9 aufweist, und wobei das in Schritt c) erhältliche Pfropfcopolymer eine Partikelgröße von 3000 ∼ 6000 Å und wobei eine wässrige Lösung davon einen pH von 8 ∼ 11 aufweist.
  3. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach Anspruch 1 oder 2, wobei eine wässrige Lösung des Emulgators von Schritt b) einen pH von 3 ∼ 9 aufweist, und wobei eine wässrige Lösung des Emulgators von Schritt c) iii) einen pH von 9 ∼ 13 aufweist.
  4. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach Anspruch 1, 2 oder 3, wobei der wasserlösliche Starter von Schritt a) ausgewählt ist aus der Gruppe bestehend aus Kaliumpersulfat, Natriumpersulfat und Ammoniumpersulfat.
  5. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach einem der vorhergehenden Ansprüche, bei dem der öllösliche Starter von Schritt b) und Schritt c) Cumolhydroperoxid, t-Butylhydroperoxid oder Benzoylperoxid ist.
  6. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach einem der vorhergehenden Ansprüche, bei dem das Alkylacrylatmonomer von Schritt b) ausgewählt ist aus der Gruppe bestehend aus Butylacrylat, Ethylacrylat und Methylacrylat.
  7. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach einem der vorhergehenden Ansprüche, wobei die aromatische Vinylverbindung von Schritt b) ausgewählt ist aus der Gruppe bestehend aus Styrol, α-Methylstyrol und Vinyltoluol.
  8. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach einem der Ansprüche 1 bis 6, bei dem die Vinylcyanidverbindung von Schritt b) Acrylnitril oder Methacrylnitril ist.
  9. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach einem der vorhergehenden Ansprüche, wobei das Alkyl(methyl)acrylat von Schritt b) ausgewählt ist aus der Gruppe bestehend aus Methyl(meth)acrylat, Ethyl(meth)acrylat, Propyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, Decyl(meth)-acrylat, und Lauryl(meth)acrylat.
  10. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach einem der vorhergehenden Ansprüche, bei dem die Polymerisationsreaktion von Schritt b) so durchgeführt wird, dass diese ferner 0,01 bis 0,07 Gewichtsanteile eines Pfropfmittels ausgewählt aus der Gruppe bestehend aus v) Arylmethacrylat (AMA), Triarylisocyanurat (TAIC), Triarylamin (TAA) und Diarylamin (DAA) enthält.
  11. Verfahren zur Herstellung von wetterbeständigem thermoplastischen Harz nach einem der vorhergehenden Ansprüche, bei dem die Polymerisationsreaktionen von Schritt a) und Schritt b) jeweils so durchgeführt werden, dass sie ferner ein Vernetzungsmittel aufweisen ausgewählt aus der Gruppe bestehend aus Ethylenglycoldimethacrylat, Diethylenglycoldimethacrylat, Triethylenglycoldimethacrylat, 1,3-Butandioldimethacrylat, 1,6-Hexandioldimethacrylat, Neopentylglycoldimethacrylat, Trimethylolpropantrimethacrylat und Trimethylolmethantriarylat.
  12. Wetterbeständiges thermoplastisches Harz hergestellt nach dem Verfahren nach einem der Ansprüche 1. bis 11.
EP01274352A 2001-07-04 2001-12-27 Verfahren zur herstellung von wetterbeständigem thermoplastischen harz Expired - Lifetime EP1337568B1 (de)

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KR2001039820 2001-07-04
KR10-2001-0039820A KR100426123B1 (ko) 2001-07-04 2001-07-04 내후성 열가소성 수지의 제조방법
PCT/KR2001/002274 WO2003004542A1 (en) 2001-07-04 2001-12-27 Methods for preparing of weatherability thermoplastic resin

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EP1337568A1 EP1337568A1 (de) 2003-08-27
EP1337568A4 EP1337568A4 (de) 2006-03-15
EP1337568B1 true EP1337568B1 (de) 2008-05-07

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US (1) US6806315B2 (de)
EP (1) EP1337568B1 (de)
JP (1) JP3955280B2 (de)
KR (1) KR100426123B1 (de)
CN (1) CN1232551C (de)
AT (1) ATE394434T1 (de)
DE (1) DE60133920D1 (de)
ES (1) ES2305032T3 (de)
WO (1) WO2003004542A1 (de)

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Publication number Priority date Publication date Assignee Title
US8969476B2 (en) * 2002-06-21 2015-03-03 Sabic Global Technologies B.V. Impact-modified compositions
US20040225034A1 (en) * 2003-05-09 2004-11-11 General Electric Company Impact-modified compositions and method
ATE338782T1 (de) * 2003-05-09 2006-09-15 Gen Electric Schlagzäh modifizierte zusammensetzungen und verfahren
DE10335958A1 (de) * 2003-08-04 2005-02-24 Basf Ag Verfahren zur Herstellung wässriger Polymerisatdispersionen
JP4398826B2 (ja) * 2003-09-25 2010-01-13 テクノポリマー株式会社 帯電防止性熱可塑性樹脂組成物及びそれを用いた成形品
KR100623850B1 (ko) * 2004-10-08 2006-09-19 주식회사 엘지화학 고무질 라텍스의 제조 방법
DE102005022635B4 (de) 2005-05-11 2018-05-30 Ineos Styrolution Europe Gmbh Thermoplastische Formmassen mit verbesserter Anfärbbarkeit
KR100809245B1 (ko) * 2005-09-28 2008-02-29 주식회사 엘지화학 아크릴레이트-스티렌-아크릴로니트릴 그라프트 공중합체,이의 제조방법 및 이를 포함하는 열가소성 수지 조성물
JP4827169B2 (ja) * 2005-10-31 2011-11-30 三菱レイヨン株式会社 プラスチゾル組成物
JP5216326B2 (ja) * 2005-12-06 2013-06-19 ポリプラスチックス株式会社 非晶性環状オレフィン系樹脂用曇り防止剤、樹脂組成物、及び光学部品
KR100828723B1 (ko) * 2006-03-09 2008-05-09 주식회사 엘지화학 기계적 물성, 내후성 및 저발연성이 우수한 열가소성 수지조성물 및 이로부터 제조된 고분자 수지 물품
KR100815995B1 (ko) * 2006-06-08 2008-03-21 제일모직주식회사 저온 및 상온 내충격성과 착색성 및 내후성이 우수한ａｓａ 그라프트 공중합체 및 이를 포함한 열가소성 수지조성물
US7953895B1 (en) * 2007-03-07 2011-05-31 Juniper Networks, Inc. Application identification
JP5144982B2 (ja) * 2007-07-27 2013-02-13 積水化成品工業株式会社 単分散粒子の製造方法
CN102344635B (zh) * 2010-08-05 2013-10-16 中国石油天然气股份有限公司 一种耐候性抗冲改性树脂的制备方法
KR20130090307A (ko) * 2012-02-03 2013-08-13 주식회사 엘지화학 아크릴계 충격보강제 및 이를 포함하는 열가소성 수지 조성물
KR101425754B1 (ko) * 2012-08-27 2014-08-05 주식회사 엘지화학 아크릴로니트릴―아크릴레이트―스티렌 그라프트 공중합체 및 이를 포함하는 열가소성 수지 조성물
CN103897110B (zh) * 2012-12-27 2016-06-08 中国石油天然气股份有限公司 一种具有耐候性苯乙烯系树脂共混物及其制备方法
US9637622B2 (en) 2013-08-20 2017-05-02 Lg Chem, Ltd. Acrylate-styrene-acrylonitrile polymer and thermoplastic resin composition
KR102075613B1 (ko) 2017-03-20 2020-02-11 주식회사 엘지화학 Asa계 그라프트 공중합체의 제조방법, 이를 포함하는 열가소성 수지 조성물의 제조방법 및 성형품의 제조방법
KR102244956B1 (ko) * 2017-11-16 2021-04-27 주식회사 엘지화학 그라프트 공중합체의 제조방법
KR102226064B1 (ko) 2018-01-24 2021-03-11 주식회사 엘지화학 열가소성 수지 조성물
KR102298295B1 (ko) * 2018-10-31 2021-09-07 주식회사 엘지화학 열가소성 수지 조성물
CN111363109A (zh) * 2020-04-26 2020-07-03 安徽金喜龙新型建材有限公司 一种抗紫外asa合成树脂瓦
KR102615118B1 (ko) 2020-07-23 2023-12-19 주식회사 엘지화학 열가소성 수지 조성물 및 이의 성형품
JP7386985B2 (ja) 2020-07-23 2023-11-27 エルジー・ケム・リミテッド 熱可塑性樹脂組成物及びその成形品
CN117304411B (zh) * 2023-11-29 2024-02-13 山东东临新材料股份有限公司 一种asa高胶粉的制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1260135B (de) 1965-01-05 1968-02-01 Basf Ag Schlagfeste thermoplastische Formmassen
US3944631A (en) * 1974-02-01 1976-03-16 Stauffer Chemical Company Acrylate-styrene-acrylonitrile composition and method of making the same
DE2826925A1 (de) * 1978-06-20 1980-01-17 Basf Ag Witterungsbestaendige, schlagzaehe thermoplastische massen mit guter einfaerbbarkeit
US4801646A (en) * 1987-01-16 1989-01-31 The Dow Chemical Company Low gloss weather and impact resistant resins
JPH04180949A (ja) 1990-11-15 1992-06-29 Asahi Chem Ind Co Ltd 良流動ａａｓ系樹脂組成物
DE4131729A1 (de) 1991-09-24 1993-03-25 Basf Ag Pfropfkautschuk-mischung und seine verwendung zur herstellung von formmassen
DE19536892A1 (de) * 1995-10-04 1997-04-10 Basf Ag Formteile aus thermoplastischen Formmassen
US5777036A (en) * 1996-02-01 1998-07-07 Basf Aktiengesellschaft Particulate graft copolymers and thermoplastic molding materials containing them and having improved colorability
FR2746672B1 (fr) 1996-04-02 1998-04-24 Atochem Elf Sa Composante catalytique et son utilisation en polymerisation des olefines
JPH10139833A (ja) 1996-11-05 1998-05-26 Techno Polymer Kk 耐候性熱可塑性樹脂の製造方法
KR19990060688A (ko) 1997-12-31 1999-07-26 김충세 내후성 및 내충격성이 향상된 아크릴계 충격보강제의 제조방법
KR20000000786A (ko) * 1998-06-03 2000-01-15 성재갑 열 가소성 수지의 제조 방법
KR100419230B1 (ko) 1998-09-02 2004-06-30 제일모직주식회사 백색도와내충격성이우수한열가소성수지의제조방법
KR100574324B1 (ko) 1999-02-04 2006-04-26 제일모직주식회사 내충격성 및 자연색상이 우수한 열가소성 수지의 제조방법
KR100497406B1 (ko) * 1999-07-16 2005-06-23 제일모직주식회사 무취 ａｂｓ수지의 제조방법 및 이를 이용한 냉장고 내상용 스티렌계 열가소성 수지 조성물
KR100428636B1 (ko) * 2000-06-01 2004-04-30 주식회사 엘지화학 저온 내충격성 및 내후성이 우수한 열가소성 수지의제조방법
KR100405306B1 (ko) * 2000-06-02 2003-11-12 주식회사 엘지화학 착색성 및 체류 광택성이 우수한 내후성 열가소성 수지의제조방법
KR100394904B1 (ko) * 2000-11-16 2003-08-19 제일모직주식회사 내후성 및 내충격성이 향상된 열가소성 수지조성물 및 그제조방법
KR100426122B1 (ko) * 2000-11-22 2004-04-08 주식회사 엘지화학 안정성이 우수한 아크릴로니트릴-부타디엔-스티렌그라프트 공중합체의 제조 방법

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JP2004521995A (ja) 2004-07-22
EP1337568A1 (de) 2003-08-27
DE60133920D1 (de) 2008-06-19
US20030153710A1 (en) 2003-08-14
WO2003004542A1 (en) 2003-01-16
ATE394434T1 (de) 2008-05-15
KR20030003950A (ko) 2003-01-14
JP3955280B2 (ja) 2007-08-08
CN1232551C (zh) 2005-12-21
EP1337568A4 (de) 2006-03-15
US6806315B2 (en) 2004-10-19

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